Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/062—Copolymers with monomers not covered by C08L33/06
  • C08L33/064—Copolymers with monomers not covered by C08L33/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/062—Copolymers with monomers not covered by C08L33/06
  • C08L33/066—Copolymers with monomers not covered by C08L33/06 containing -OH groups

Definitions

• the invention relates to water-thinnable lacquer binders based on acrylate copolymers, as well as the process for the preparation of these binders and their use for the formulation of water-thinnable top coats with a low content of organic auxiliary solvents.
• Water-dilutable binders which are obtained by mixing or partially condensing a polycarboxyl component which is water-soluble after neutralization of the carboxyl groups with a resinous, essentially non-water-dilutable polyhydroxyl component and which are distinguished by a favorable viscosity behavior when diluted with water are claimed in a number of property rights, for example in AT-PS 328 587, AT-PS 379 607, AT-PS 388 738 and AT-PS 388 382.
• AT-PS 328 587 acrylate copolymers are given as combination partners, however, based on the usual monomer composition described there, no lacquers that can be used in practice can be formulated, since these have disadvantages in their application properties, such as the tendency to form bubbles and run off during the baking process , even with thin layers.
• the invention accordingly relates to water-thinnable paint binders based on acrylate copolymers which were obtained by partial condensation of a polycarboxyl component with a polyhydroxyl component and subsequent, at least partial neutralization of the carboxyl groups, which are characterized in that as
• the invention further relates to the process for the preparation of these binders and their use for the formulation of water-dilutable topcoats with a low content of organic auxiliary solvents.
• Components (A) and (B) are prepared in a known manner by solution polymerization.
• the monomers are used in the proportions stated in the main claim.
• Monomer components (Aa) and (Ba) are (meth) acrylic acid esters of alkanols with 1 to 12 C atoms, and optionally in proportions, ie up to 50% by weight. aromatic vinyl monomers, especially styrene, are also used.
• the components (Ab) and (Bf) preferably consist of acrylic or methacrylic acid, but other ⁇ , ⁇ -ethylenically unsaturated carboxylic acids, such as maleic acid, can optionally also be used.
• component (Bb) monoesters of (meth) acrylic acid with diols which have 2 to 4 carbon atoms, such as ethylene glycol, propylene glycol and butylene glycol or the corresponding isomeric compounds, are used. It is also possible to use monoesters of alkane diols containing 6 to 12 carbon atoms, for example tri- or corresponding polyethylene glycol mono (meth) acrylic acid esters or di- or corresponding polypropylene mono (meth) acrylic acid esters.
• the components (Ac) and (Bc) consist of multifunctional copolymerizable monomers, such as butanediol di (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate or divinylbenzene.
• Thioglycolic acid esters such as pentaerythritol tetrathioglycolic acid esters or glycerol trithioglycolic acid esters are used as multifunctional chain termination regulators (Ad) and (Bd).
• Perfluorooctylethyl methacrylate or similar monomers are preferably used as fluorine-containing monomers for components (Ae) and (Be).
• the polycarboxyl component (A) must have an acid number of 70 to 240 mg KOH / g, preferably 100 to 200 mg KOH / g.
• the hydroxyl number of the polyhydroxyl component (B) is between 90 to 250 mg KOH / g, preferably between 110 and 180 mg KOH / g, the acid number optionally between 10 and 30 mg KOH / g.
• Components (A) and (B) are mixed in a ratio, based on solids content, between 10:90 and 40:60.
• the solvent of the polymers is then largely removed under vacuum and, if necessary, replaced by a water-tolerant, high-boiling auxiliary solvent, such as alcohols or glycol ethers.
• the partial condensation takes place at 100 to 150 ° C., preferably at 110 to 130 ° C., until the intrinsic viscosity (measured in chloroform / 20 ° C.) has risen to 12 to 18 ml / g, preferably to 13 to 16 ml / g .
• the ratio of the intrinsic viscosity of the condensation product to the starting mixture should be 1.1: 1 to 1.7: 1, preferably 1.2: 1 to 1.5: 1.
• a suitable neutralizing agent such as ammonia, secondary and tertiary amines or alkanolamines, is added and the batch is diluted to the desired solids content with deionized water.
• the largely anhydrous, optionally partially or completely neutralized condensation product from components (A) and (B) is added a hydrophobic amino resin, preferably before the addition of the optionally required neutralizing agent and before dilution with water as crosslinking component (C) Melamine-formaldehyde resin, in a proportion of 15 to 35% by weight, preferably 20 to 30% by weight, based on the solids content of the total binder, mixed in at a maximum of 85 ° C. and thoroughly homogenized.
• the hydrophobic amino resins used as component (C) according to the invention are selected by a simple dilutability test.
• Melamine resins, benzoguanamine resins and urea resins are suitable which, in a mixture of 25 parts by weight of the resin in the delivery form, 15 parts by weight of ethylene glycol monobutyl ether and 85 parts by weight of water, give rise to a greater turbidity or at room temperature no later than 5 minutes after the mixture Show segregation.
• a large number of products of this type are commercially available.
• CYMEL® 1158/80 CYMEL® 254/80 (both AMERICAN CYANAMID CO), VIAMIN® MF 514/60 (VIANOVA) or MAPRENAL® MF 915/75 (HOECHST) have proven to be useful, for example.
• VIAMIN® MF 514/60 VIAMIN® MF 514/60
• MAPRENAL® MF 915/75 HOECHST
• the binders according to the invention are suitable for oven-drying topcoats, such as automotive topcoats, electrical equipment lacquers and similar fields of application. Above all, they can also be used to formulate clearcoats using the base coat / clear coat method for automotive top coats.
• the possibility of formulating paints with a very low content of organic auxiliary solvents with the binders according to the invention is of considerable advantage.
• copolymers were prepared in a known manner by solution polymerization in isopropanol, corresponding to a calculated solids content of 50% by weight for components (A) and 65% by weight for components (B). Quantities and key figures are summarized in Table 1.
• Components (A) and (B) are mixed in the proportions given in Table 2.
• the isopropanol is removed under vacuum until the solids content of the batch is at least 95% by weight.
• condensation is carried out at 110 to 120 ° C. until the desired intrinsic viscosity is reached.
• the mixture is cooled to 95 ° C., neutralized with amine and dispersed well with deionized water.
• component (C) is mixed in after the neutralization with the amine, the batch being homogenized for at least 10 minutes at a maximum of 85 ° C. and then adjusted to the desired solids content with deionized water.
• the binders according to the invention were tested as clear lacquers in a metal effect base coat clear coat system and as white lacquers.
• the paint batches were adjusted to a pH of 7.5 to 9.0 using dimethylethanolamine and diluted to a viscosity of 27 to 30 seconds in accordance with DIN 53211/23 ° C. using deionized water.
• the clearcoats were applied to coated steel sheets (zinc phosphating, cathodically deposited electrocoat material (a), filler (b), metal effect base coat (c), products (a) to (c) used in the automotive industry being used) by Syringes at 23 ° C and 60% rel. Humidity. After a flash-off time of 10 minutes and a predrying time of 10 minutes at 80 ° C, the paints were baked at 140 ° C for 30 minutes.
• the white lacquers were applied and baked in an analogous manner to coated steel sheets (zinc phosphating, cathodically deposited electrodeposition lacquer (a), filler (b), products used in the automotive industry being used as (a) and (b)).

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Paints Or Removers (AREA)

Applications Claiming Priority (4)

Publications (2)

Family

ID=25593920

Family Applications (1)

Country Status (5)

Cited By (2)

Families Citing this family (5)

Citations (1)

• 1991
  • 1991-04-16 AT AT0079091A patent/AT397508B/de not_active IP Right Cessation
  • 1991-12-16 EP EP19910121525 patent/EP0496079A3/de not_active Withdrawn
  • 1991-12-23 CA CA002058371A patent/CA2058371A1/fr not_active Abandoned
  • 1991-12-26 JP JP3345611A patent/JPH04304277A/ja not_active Withdrawn
  • 1991-12-27 KR KR1019910024696A patent/KR920012342A/ko not_active Application Discontinuation

Patent Citations (1)

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